Wetting and anti-foaming agent

ABSTRACT

A wetting agent according to Formula (I): 
     
       
         
         
             
             
         
       
         
         
           
             wherein R 1  is selected from a branched alkyl group or linear alkyl group or a cycloaliphatic group or an aromatic group, each having 6 to 15 carbon atoms; R 2  is selected from hydrogen, methyl, or ethyl; R 3  is selected from hydrogen, methyl, or ethyl; R 4  is selected from hydrogen, methyl, or ethyl; R 5  is selected from methyl or ethyl; x ranges from 0 to 5; y ranges from 0 to 10; z ranges from 1 to 10; with the proviso that when x ranges from 1 to 5, R 2  is different from R 3 ; and with the proviso that when x=0, R 3  is different from R 4 . The wetting agent also imparts anti-foam properties to aqueous solutions while reducing surface tension.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority benefit from U.S. Provisional PatentApplication 62/238,260 filed Oct. 7, 2015 which is incorporated byreference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates to use of multifunctional alkoxylatecompositions as dual wetting and anti-foaming agents.

BACKGROUND OF INVENTION

The ability to reduce the surface tension of water is important forwaterborne coating formulations as decreased surface tension leads toenhanced substrate wetting particularly for hydrophobic surfaces.Static- and dynamic surface tension are important measures of theability of a wetting agent to reduce surface tension in aqueous systems.

Traditional nonionic surfactants, such as alkylphenol or alkylethoxylates and ethylene oxide (EO)/propylene oxide (PO) copolymers, andanionic surfactants, such as sodium dialkyl sulfosuccinates, exhibitacceptable static surface tension properties. However, many of thesesurfactants create foam, which can lead to surface defects, pooradhesion, and processing difficulties.

SUMMARY OF INVENTION

In an embodiment, the invention provides for a wetting agent comprisinga composition according to Formula (I):

wherein R¹ is selected from a branched alkyl group, a linear alkyl groupor a cycloaliphatic group or an aromatic group, each having 6 to 15carbon atoms; R² is selected from hydrogen, methyl, or ethyl; R³ isselected from hydrogen, methyl, or ethyl; R⁴ is selected from hydrogen,methyl, or ethyl; R⁵ is selected from methyl or ethyl; x ranges from 0to 5; y ranges from 0 to 10; z ranges from 1 to 10; with the provisothat when x ranges from 1 to 5, R² is different from R³; and with theproviso that when x=0, R³ is different from R⁴.

In another embodiment, the wetting agent according to Formula (I),further comprising a composition according to Formula (II):

wherein R⁶ is the same as R¹, R⁷ is the same as R², R⁸ is the same as R³and R⁹ is the same as R⁴, a equals x, b equals y and c equals z.

In one embodiment of the wetting agent according to Formula (I), R¹ isselected from a branched alkyl group or linear alkyl group or acycloaliphatic group or an aromatic group, each having 6 to 10 carbonatoms.

In one embodiment of the wetting agent according to Formula (I), R¹ isselected from nonyl, iso-nonyl, 3,5,5-trimethyl hexyl, octyl, 2-methylheptyl, 2-ethyl hexyl, 2,2,4-trimethyl pentyl, 4-methyl pentyl, heptyl,hexyl and combinations thereof. In one such embodiment, x is zero, yranges from 2 to 5, z ranges from 3 to 10, R³ is hydrogen or methyl andR⁴ is hydrogen or methyl.

In various embodiments, a 0.3 wt. % solution of the wetting agentcomposition in deionized water has a measured dynamic surface tensionranging from: 50 mN/m to 25 mN/m; 45 mN/m to 25 mN/m; 40 mN/m to 25mN/m; or 35 mN/m to 25 mN/m each at a surface age of 1000 ms or less.

In other various embodiment, a 0.3 wt. % solution of the wetting agentcomposition in deionized water has a measured dynamic surface tensionranging from: 50 mN/m to 25 mN/m; 45 mN/m to 25 mN/m; 40 mN/m to 25mN/m; or 35 mN/m to 25 mN/m each at a surface age of 30,000 ms.

In other various embodiments, a 0.3 wt. % solution of the wetting agentin deionized water has a static surface tension ranging from: 45 mN/m to25 mN/m; 40 mN/m to 25 mN/m; or 35 mN/m to 25 mN/m.

The present invention further provide an embodiment for a method fordefoaming and/or for preventing foaming of liquid media, comprisingmixing the an embodiment of wetting agents described herein, an emulsionthereof, or a powder thereof, with the liquid media.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing summary, as well as the following detailed description ofthe invention, will be better understood when read in conjunction withthe appended drawings.

The FIGURE illustrates a plot of surface age versus surface tension forvarious inventive compositions described herein.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present disclosure provides for a dual wetting and anti-foam agent.

In an embodiment, the invention provides for a wetting agent comprisinga composition according to Formula (I):

wherein R¹ is selected from a branched alkyl group, a linear alkyl groupor a cycloaliphatic group or an aromatic group, each having 6 to 15carbon atoms; R² is selected from hydrogen, methyl, or ethyl; R³ isselected from hydrogen, methyl, or ethyl; R⁴ is selected from hydrogen,methyl, or ethyl; R⁵ is selected from methyl or ethyl; x ranges from 0to 5; y ranges from 0 to 10; z ranges from 1 to 10; with the provisothat when x ranges from 1 to 5, R² is different from R³; and with theproviso that when x=0, R³ is different from R⁴.

In another embodiment, the wetting agent according to Formula (I),further comprising a composition according to Formula (II):

wherein R⁶ is the same as R¹, R⁷ is the same as R², R⁸ is the same as R³and R⁹ is the same as R⁴, a equals x, b equals y and c equals z.

In such embodiments, wetting agents comprising compositions according toFormula I and Formula II that may contain varying amounts of suchcompounds according to: 50 wt. % Formula I and 50 wt. % Formula II; 60wt. % Formula I and 40 wt. % Formula II; 75 wt. % Formula I and 25 wt. %Formula II; 85 wt. % Formula I and 15 wt. % Formula II; 95 wt. % FormulaI and 5 wt. % Formula II.

In some other embodiments, wetting agents comprising compositionsaccording Formula (I) and Formula (II) may contain varying amounts ofsuch compounds according to: 50 wt. %-99 wt. % Formula I and 1 wt. % to50 wt. % Formula II; 60 wt. %-99 wt. % Formula I and 1 wt. % to 40 wt. %Formula II; 70 wt. %-99 wt. % Formula I and 1 wt. % to 30 wt. % FormulaII; 80 wt. %-99 wt. % Formula I and 1 wt. % to 20 wt. % Formula II; 90wt. %-99 wt. % Formula I and 1 wt. % to 10 wt. % Formula II; 95 wt. %-99wt. % Formula I and 1 wt. % to 5 wt. % Formula II.

In one embodiment of the wetting agent according to Formula (I), R¹ isselected from a branched alkyl group or linear alkyl group or acycloaliphatic group or an aromatic group, each having 6 to 10 carbonatoms.

In one embodiment of the wetting agent according to Formula (I), R¹ isselected from nonyl, iso-nonyl, 3,5,5-trimethyl hexyl, octyl, 2-methylheptyl, 2-ethyl hexyl, 2,2,4-trimethyl pentyl, 4-methyl pentyl, heptyl,hexyl and combinations thereof. In one such embodiment, x is zero, yranges from 2 to 5, z ranges from 3 to 10, R³ is hydrogen or methyl andR⁴ is hydrogen or methyl.

In embodiments of the foregoing wetting agents, a 0.3 wt. % solution ofthe wetting agent composition in deionized water has a measured dynamicsurface tension ranging from: 50 mN/m to 25 mN/m; 45 mN/m to 25 mN/m; 40mN/m to 25 mN/m; or 35 mN/m to 25 mN/m each at a surface age of 1000 msor less.

In other embodiments of the foregoing wetting agents, a 0.3 wt. %solution of the wetting agent composition in deionized water has ameasured dynamic surface tension ranging from: 50 mN/m to 25 mN/m; 45mN/m to 25 mN/m; 40 mN/m to 25 mN/m; or 35 mN/m to 25 mN/m each at asurface age of 30,000 ms.

In other embodiments of the foregoing wetting agents, a 0.3 wt. %solution of the wetting agent in deionized water has a static surfacetension ranging from: 45 mN/m to 25 mN/m; 40 mN/m to 25 mN/m; or 35 mN/mto 25 mN/m.

In embodiments of the foregoing wetting agents, a 0.3 wt. % solution ofthe wetting agent in aqueous solution has a foaming value less than 17cm when measured at a concentration of 0.3 wt. % according to the foamtest procedure described herein, and has a foaming value less than 3 cmwhen measured at a concentration of 0.3 wt. %, at 5 minutes aftercompletion of the foam test procedure. In another embodiment, thepresent invention provides for an aqueous composition comprising aneffective amount of any of the foregoing wetting agents in deionizedwater wherein the wetting agent also acts as an anti-foam agent. Inembodiments of the aqueous composition, an effective amount of any ofthe foregoing wetting agents ranges from: 0.01 wt. % to 7.0 wt. %; 0.1wt. % to 5.0 wt. %; 0.1 wt. % to 3.0 wt. %; 0.1 wt. % to 1.0 wt. %; and0.1 wt. % to 0.5 wt. %.

In one such embodiment, the aqueous composition has a foaming value lessthan 17 cm when measured at a concentration of 0.3 wt. % according tothe foam test procedure, described herein, and has a foaming value lessthan 3 cm when measured at a concentration of 0.3 wt. % 5 minutes aftercompletion of the foam test procedure. In another such embodiment, theaqueous composition has a foaming value less than 10 cm when measured ata concentration of 0.3 wt. % according to the foam test procedure,described herein, and has a foaming value less than 1 cm when measuredat a concentration of 0.3 wt. %, at 5 minutes after completion of thefoam test procedure. In yet another such embodiment, the aqueouscomposition has a foaming value less than 5 cm when measured at aconcentration of 0.3 wt. % according to the foam test procedure,described herein, and has a foaming value less than 1 cm when measuredat a concentration of 0.3 wt. %, at 5 minutes after completion of thefoam test procedure. In still yet another such embodiment, the aqueouscomposition has a foaming value less than 2 cm when measured at aconcentration of 0.3 wt. % according to the foam test procedure,described herein, and has a foaming value less than 1 cm when measuredat a concentration of 0.3 wt. %, at 5 minutes after completion of thefoam test procedure. In a particular such embodiment, the aqueouscomposition has a foaming value of 0 cm when measured at a concentrationof 0.3 wt. % according to the foam test procedure, described herein, andhas a foaming value of 0 cm when measured at a concentration of 0.3 wt.%, at 5 minutes after completion of the foam test procedure.

Each of the foregoing embodiments of aqueous composition wherein thewetting agent also acts as an anti-foam agent, the wetting agent alsoprovides static tension control. In some such embodiments, a 0.3 wt. %solution of the wetting agent composition in deionized water has ameasured dynamic surface tension ranging from: 50 mN/m to 25 mN/m; 45mN/m to 25 mN/m; 40 mN/m to 25 mN/m; or 35 mN/m to 25 mN/m each at asurface age of 1000 ms or less.

In other such embodiments, a 0.3 wt. % solution of the wetting agentcomposition in deionized water has a measured dynamic surface tensionranging from: 50 mN/m to 25 mN/m; 45 mN/m to 25 mN/m; 40 mN/m to 25mN/m; or 35 mN/m to 25 mN/m each at a surface age of 30,000 ms. In stillother embodiments, a 0.3 wt. % solution of the wetting agent indeionized water has a static surface tension ranging from: 45 mN/m to 25mN/m; 40 mN/m to 25 mN/m; or 35 mN/m to 25 mN/m. In other embodiments ofthe foregoing aqueous compositions, the aqueous composition comprises alatex polymer. In other embodiments of the foregoing aqueouscompositions, the aqueous composition comprises a pigment.

In other embodiments of the foregoing aqueous compositions, theforegoing embodiments of wetting agents may be used with polymericbinder which may be either solvent or water borne. Waterborne binder istypically in the form of discrete solid polymeric particles formed bythe polymerization of at least one ethylenically-unsaturated monomer inan aqueous dispersion medium. The polymeric particles are typicallyformed by emulsion polymerization in accordance with known technology.

Representative polymeric particles that are suitable for the aqueouscomposition include acrylic polymers, vinyl acetate polymers, vinylchloride polymers, acrylic urethanes, water reducible alkyds, alkydemulsions, styrene acrylic, VAE and combinations thereof. Suitableacrylic polymers include copolymers of acrylonitrile, acrylic acid,methacrylic acid, butylacrylic acid, butyl acrylates, ethyl acrylates,methyl methacrylate, vinyl acetate, styrene, and combinations thereof.

In another embodiment of the foregoing aqueous compositions, theforegoing embodiments of wetting agents may be used in aqueouscomposition comprising a pigment which may be either organic orinorganic. A wide range of pigments may be included in the composition.Suitable pigments include inorganic pigments such as titanium dioxide,pigmentary iron oxide (Fe₂O₃) and organic pigments including bluepigments, green pigments, yellow pigments arylide yellow, Hansa® Brightyellow, red pigments, quinacridone red, violet pigments, orange pigmentsand similar materials.

In another embodiment of the foregoing aqueous compositions, theforegoing embodiments of wetting agent may be used in coating which maybe either solvent or waterborne. For example, water borne coating mayinclude adhesion promoters, rheology modifiers, dispersing agents,defoamers, biocides, fillers, pH control additives, open time extenders,and polymer which is typically a water-based latex component, and thecoating composition may be referred to as “latex-based” paint.

In other embodiments of the foregoing wetting agent, the wetting agentmay be used in water based, solvent based, or solvent free formulationsfor industrial coatings, automotive coatings, adhesives, and sealantapplications for the purposes of facilitating substrate wetting, pigmentwetting by the resin or solvent, and improving compatibility multiphasecompositions in such as an epoxy containing rubber particles. Examplesof adhesives and sealant resin types include epoxy, polyurethane,acrylic, MS Polymer™, SPUR polymer, styrene-budiene, styrene-phenolic,polylactic acid, polyaspartic acid, ethylene propylene diene terpolymer(EPDM), polysiloxane, polyurea, cementitious, and also hybridcombinations of the resins such as epoxy-silane coating products.

In other embodiments of the foregoing wetting agent, the wetting agentmay be used in powder coatings for the purposes of facilitatingsubstrate wetting, pigment wetting by the resin or solvent, andimproving compatibility multiphase compositions in such as an epoxyformulation also containing a urethane resin. Examples of powder coatingresins include acrylic, polyester, epoxy, polyanhydride, unsaturatedresins for UV curing, glycoluril, and hybrids combinations such asacrylic-epoxy products.

In another embodiment, the invention provides for a method for defoamingand/or for preventing foaming of liquid media by mixing the liquidmedium with any of the foregoing embodiments of the wetting agentdescribed herein, an emulsion thereof, or a powder thereof. In some suchembodiments, the liquid media comprises a latex polymer. In other suchembodiments, the liquid media comprises a pigment.

The various embodiments of wetting agents, described herein, may beprepared in a sequential manner. In one example, the wetting agent maybe prepared by a first propoxylation step where oxypropylene moieties(“PO”) are attached to an alcohol or mixture of alcohols to form a POblock. After the propoxylation step, oxyethylene moieties (“EO”) areadded to form an EO block attached to the PO block. Subsequent to theethoxylation step, an organic moiety is added as an end group. Organicmoieties include trimethysilyl and trifluoromethyl and similar. Inanother example, the wetting agent may be prepared by a firstethoxylation step where oxyethylene moieties (“EO”) are attached analcohol or mixture of alcohols to form an EO block. After theethoxylation step, oxypropylene moieties (“PO”) are added to form a POblock attached to the EO block. Subsequent to the propoxylation step, anorganic moiety is added as an end group. In another example, the wettingagent may be prepared by a first ethoxylation step where oxyethylenemoieties (“EO”) are attached an alcohol or mixture of alcohols to forman EO block. After the ethoxylation step, oxypropylene moieties (“PO”)are added to form a PO block attached to the EO block. After thepropoxylation step, oxyethylene moieties (“EO”) are added to form an EOblock attached to the PO block. Subsequent to the ethoxylation step, anorganic moiety is added as end group. In preceding examples individualoxypropylene moieties (“PO”) can be exchanged for oxybutylene moieties(“BO”) to form a BO block. This method can be used to make all possiblepermutations as described in Formula I and Formula II.

Description of Test Methods

A variety of methods may be used to characterize the physical propertiesof exemplary wetting agent compositions and aqueous compositions. Themethods are described below.

Wetting Agent Aqueous Solution Evaluation Foam Test Procedure

In a clean glass container, 0.3 grams of wetting agent and 99.70 gramsof deionized water were mixed for two minutes and then 50 mL of themixture was poured in a 250 mL graduated cylinder. A clean air bubblediffuser stone (Penn Plax Air Stone, 7/16″ Cylinder, Model AS6B) wasattached to rubber tubing that was attached to a Maxima air pump model #A-805 which supplies air at 2.5 psi with a flow rate: 2300-2500 cc/min.This is the actual flow rate with the diffuser stone in place andsubmerged in 50 mL of 0.3 wt. % wetting agent in deionized water. Theair bubble diffuser stone was placed in the graduated cylinder filledwith the aqueous solution. Air is pumped into the aqueous solution for30 seconds or in case of foaming solutions at a reduced time until theheight reaches 250 ml. The air supply is then stopped.

The height of the bubbling solution is recorded immediately afterremoving air source and at set time intervals until solution heightreturns to 50 ml or stabilizes. For the foam test procedure, the 200 mLmark, of a 250 mL graduated cylinder, equals 17 cm±0.2 cm.

Surface Tension Reduction

Static Surface Tension (SST) may be measured by someone skilled in theart, with a surface tensiometer (i.e. Kruss™ K100 Tensiometer) using theWilhelmy Plate method. Static Surface Tension (SST) measurementsdemonstrate the lowest surface tension that a wetting agent can achievein solution independent of kinetic mobility restrictions that particularsurfactants may have. This is an indicator of the surface tensionreducing capability of a wetting agent. The Wilhelmy Plate method forevaluating SST is a well-established method in the industry and was usedto measure the surface tension produced by the wetting agents describedherein.

Dynamic Surface Tension (DST) may be measured by someone skilled in theart with a bubble tensiometer (i.e. Kruss™ BP2 Bubble Tensiometer).Dynamic surface tension (DST) measurements allow for the assessment of awetting agent's intrinsic ability to reduce interfacial surface tension.DST measures the surface tension of aqueous solutions of the wettingagent over a range of surface ages generated by bubbling gas into thesolutions at different rates. By varying the rate of bubbling, differentages of bubble surfaces are created, and the instrument determines thesurface tension at each of these different rates and reveals intrinsickinetic mobility restrictions that particular wetting agents may have.Kinetic mobility restrictions can limit a wetting agent's wettingperformance when the application speed exceeds the mobility limits ofthe wetting agent. Short surface ages (10 ms) relate to rapid dropletformation which might occur during spray atomization. Long surface ages(30,000-50,000 ms) may relate closer to brushing type coatingapplications and levelling. This technique generates a characteristiccurve profile for a wetting agent over the range of surface ages in thetest.

Water Droplet Spreading

Plastic panels were used as substrates for depositing the aqueoussolutions. The panels were 4″×6″ (95 mm×145 mm) Dow Pulse 2000 blackPC/ABS panels. The glossy side was wiped with IPA using a paper toweland allowed to air dry. Solutions of each of wetting agent were preparedahead of time at 0.3% concentration by weight in deionized water. Ablank solution containing only deionized water was tested as a baselinereference.

The deposition of the aqueous solutions on the panels was performed asfollows: A separate panel was used for each tested solution. Syringeswith attached needles were used to deposit the solutions (B-D 1cc25G 5/8Tuberculin Syringe & Precision Glide Needle—Part 9626). The solutionswere drawn up in the syringe until they contained precisely 1.0 ml ofthe solution. The syringe was placed vertically in the center of thetest panel on the bench, with the syringe tip oriented perpendicularlyand placed in direct contact resting on the surface of the panel. Theplunger was steadily pressed down and the liquid was deposited slowlyover 15 sec. on the test panel where the needle was positioned. Thesolutions were allowed to sit undisturbed to equilibrate and spread for3-4 min. Deionized H₂O is used as the reference blank. The solutionswhich spread significantly did not have symmetrical areas. Theirdimensions (L×W) were then measured with a ruler.

Photographs of the water droplets spreading pattern on the panels weretaken using a Sony DSC-HX10V digital camera. The photos were taken at anangle inside a MM-1 GTI MiniMatcher light booth (GTI Graphic Technology)in order to overcome the challenge of being able to see the cleartransparent liquid patterns on top of the black glossy panel surface.Their dimensions (L×W) were measured with a ruler and are reported.

Coating Evaluation Test Methods for Examples 24-26

ASTM D523: Gloss Measurement was followed using BYK Micro Trigloss meter

ASTM D562: Stormer Viscosity ASTM D714: Blister Resistance ASTM D6736Early Block Resistance ASTM D1849: Storage Stability ASTM D2486: ScrubResistance ASTM D4062: Leveling ASTM D4287: Cone & Plate ICI ASTM D4400:Sag Resistance ASTM D4828: Washability ASTM D 6736: Burnish Resistance

ASTM D7190: Surfactant leachingASTM D8020: Freeze Thaw stabilityModifications that were Made to the ASTM MethodsD4287 Cone & Plate ICI testing was followed except that the hold timewas 5 seconds instead of 30 seconds.D523 Gloss Measurement was followed using BYK Micro Trigloss meter.D6736 Burnish Resistance was followed except that the cheesecloth waswrapped around a dry sponge which was inserted into the sponge holderbefore the machine was turned on.D8020 Freeze Thaw stability—Wetting agents were added at 0.60% on totalpaint weight to differentiate their advantage on freeze thaw stability.Samples were mixed on Red Devil shaker and tested for paint uniformityand smoothness. Paints that were uniform and smooth were rated pass.Paints that gelled and could not be mixed after shaking to uniformconsistency were rated as fail.

Test A1: Roller Foaming

Foaming tendency of a wetting agent was tested by roller application.This was achieved by pouring approximately 5 to 10 grams of test samplesside by side directly onto a Leneta Sag and Flow chart (Form 7B) andthen making one downward pass with the roller through the slurry using a9″ wide ⅜″ nap Purdy roller. The amount of foam generated was visuallyassessed and qualitatively ranked against the control (without wettingagent) using the following rating: 10—Excellent; 7—Good; 4—Fair; 1—Poor.

Test A2: Brush Foaming

Foaming tendency of wetting agent was carried out by taking a 2″ flatGen X Chinex brush that was dipped into a container with the test sampleand applying three brush strokes to a Leneta Sag and Flow chart (Form7B). The resulting foam in the film was visually assessed andqualitatively ranked against control (without wetting agent) using thefollowing rating: 10—Excellent; 7—Good; 4—Fair; 1—Poor.

Test B: Roller Stability

250 grams of the test sample was placed in a ½ pint container andsubjected to mechanical agitation (roller) by using an agitator @ 153rpm for a period of 24 hours and 12 days.

Test Method C: Color Acceptance

Color acceptance was measures using 8 oz of colorant/gallon of paint.The colorant was Colortrend Lamp Black 808B. The test paint is describedin Example 26.

Test Method D: Blush/Color change upon water contactTest panels were cured for 24 hours at 25° C. They were then subjectedto water contact for 2 hours and visually assessed for color change.Test Method E: Tint strength test methodPurpose: to determine relative tint strength of a white pastel basepaint.The formulation of the base paint is described in Example 26. Tintstrength was measures using 2 oz of colorant/gallon of paint. Thecolorant was Colortrend Lamp Black 808B. Tint strength was measuredusing a Datacolor Colorimeter.Procedure for Tint strength

-   -   1. Prepare a tinted paint as per above at 2 oz colorant per        Gallon of paint.    -   2. Place on Red devil shaker for 5 minutes.    -   3. Allow to rest in a controlled temperature cabinet or water        bath at 25° C. for 30 minutes    -   4. Prepare a side by side drawdown with the control paint which        has been tinted in the same way using a 3 mil Bird bar on a        Penopac chart (e.g., Leneta Form 1B)    -   5. Allow to dry in a controlled temperature and humidity        environment (25±5° C.; 50±5% humidity).    -   6. Measure tint strength of the test sample and compare to        control paint.

Test Method F: Substrate Wettability

The wetting ability of wetting agent was carried out by taking a 2″ flatGen X Chinex brush that was dipped into a container with the test sampleand applying minimum amount of test sample with brush held perpendicularto the substrate and dragging it to generate brush marks. Allow 5 mins.for the sample to flow and then asses the substrate for film defects.The resulting wetting defects manifested as crawling in the film wasvisually assessed and qualitatively ranked against control (withoutwetting agent) using the following rating: 10—Excellent; 7—Good; 4—Fair;1—Poor.

EXAMPLES

The following examples further describe and demonstrate illustrativeembodiments within the scope of the present invention. The examples aregiven solely for illustration and are not to be construed as limitationsof this invention as many variations are possible without departing fromthe spirit and scope thereof.

Example 1

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,2-ethylhexanol (1020.9 g) was charged. A solution of 50 wt % KOH inwater (8.8 g) was added and the mixture was heated to 120° C., whilesparging with nitrogen. Water was removed during 2.5 hours under theseconditions, the final water concentration was 0.06 wt %, with a totaldistillate weight of 16.3 g. Propylene oxide (887 g) was added at 120°C. during ±1.5 hours. After addition was complete the reaction mixturewas held at 120° C. until the pressure was stable (±2 hours). Themixture was heated to 140° C. and ethylene oxide (1346 g) was addedduring ±2 hours. After addition was complete the reaction mixture washeld at 140° C. until the pressure was stable (±0.5 hours). The reactionmixture was cooled to 50° C. and removed from the reactor, yielding 3217g of a clear, colorless liquid. OH value: 131.26 mg KOH/g; Acid value:0.06 mg KOH/g; pH (1% in water): 6.6.

Example 2

A four-necked, 500 mL round bottom flask was fitted with a mechanicalstirrer, a thermometer, a stopper and a reflux condenser topped with agas inlet tube. The round bottom flask was charged with Example 1 (100g) and para-toluenesulfonic acid monohydrate (1.8 g). Methylal (200 g)was charged in one addition. The mixture was refluxed at ±50° C. for 12hours. Sodium carbonate (0.5 g) in water (5 mL) was added and theresulting mixture was stirred for 30 minutes. The mixture was filteredthrough celite, after which all volatiles were removed at reducedpressure (30 mbar, 50° C.), yielding 107.34 g of a cloudy, colorlessliquid. OH value: 32.8 mg KOH/g; Acid value: 1.1 mg KOH/g; pH (1% inwater): 4.6.

Example 3

In a 500 ml, four-necked round bottom flask, filled with a nitrogenatmosphere and equipped with a mechanical stirrer, a thermometer, areflux condenser and a gas inlet tube, para-toluenesulfonic acidmonohydrate (1.88 g) was dissolved in Example 1 (100 g). The mixture wasstirred at room temperature and dimethoxymethane (200.00 g) was added inmultiple aliquots. Between additions of dimethoxymethane aliquots, themixture was alternatively heated to reflux followed by vacuumdistillation, at ±30 mbar and 55-60° C., to remove volatiles. Themixture was reacted for 12 hours. Sodium carbonate (1.05 g) wasdissolved in the minimum amount of water (±5 mL) and added to thereaction mixture. White solid precipitated out of solution. Allvolatiles were removed under reduced pressure. The resulting mixture wasfiltered, yielding 107.34 g of a cloudy, colorless liquid. OH value:32.8 mg KOH/g; Acid value: 1.1 mg KOH/g; pH (1% in water): 4.6.

Example 4

In a clean and dry, 1 liter, glass pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a butylene oxide inlet, athermometer and a pressure sensor, 4-methyl-2-pentanol (771.8 g) wascharged. Sodium methanolate (2.32 g) was added and the mixture washeated to 100-125° C. The reactor was opened to the atmosphere and,while sparging with nitrogen, methanol was deionized off during ±2hours. The reactor was closed, the mixture heated to 130-140° C. andbutylene oxide (423 g) was added over 12 hours. The mixture was cooledto room temperature and discharged from the reactor yielding 506.8 g ofa brown liquid. OH value: 171.8 mg KOH/g; Acid value: 3.2 mg KOH/g; pH(1% in water): 10.3. The brown liquid (359.8 g) was transferred to aclean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor. Themixture was sparged with nitrogen and heated to 140° C. for 30 minutes.Ethylene oxide (194 g) was added at 140° C. during about 0.5 hours.After addition was complete the reaction mixture was held at 140° C.until the pressure was stable (±0.5 hours). The reaction mixture wascooled to 50° C. and neutralized with 0.63 g acetic acid. 192 g of abrown liquid was removed from the reactor: OH value: 110 mg KOH/g; Acidvalue: 0.2 mg KOH/g; pH (1% in water): 5.9.

Example 5A

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,2-ethylhexanol (771.8 g) was charged. A solution of 50 wt % KOH in water(8.9 g) was added and the mixture was heated to 120° C., while spargingwith nitrogen. Water was removed during 2.5 hours under theseconditions, the final water concentration was 0.08 wt %, with a totaldistillate weight of 21.8 g. Propylene oxide (662 g) was added at 120°C. during ±1.5 hours. After addition was complete the reaction mixturewas held at 120° C. until the pressure was stable (±2 hours). Themixture was heated to 140° C. and ethylene oxide (1506 g) was addedduring ±2 hours. After addition was complete the reaction mixture washeld at 140° C. until the pressure was stable (±0.5 hours). The reactionmixture was cooled to 40° C. and 944.1 g of a clear colorless liquid wasremoved from the reactor, which was neutralized with 3.68 g acetic acid:OH value: 112.9 mg KOH/g; Acid value: 0.13 mg KOH/g, pH (1% in water):6.0.

Example 5B

The product mixture remaining in the reactor, from Example 5A, washeated to 140° C. and 339 g of ethylene oxide was added over ±0.25hours. After addition was complete the reaction mixture was held at 140°C. until the pressure was stable (±0.5 hours). The reaction mixture wascooled to 40° C. and 907 g of a clear colorless liquid was removed fromthe reactor, which was neutralized with 3.05 g acetic acid: OH value:96.4 mg KOH/g; Acid value: 0.12 mg KOH/g, pH (1% in water): 6.1.

Example 5C

The product mixture remaining in the reactor, from Example 5A, washeated to 140° C. and 205 g of ethylene oxide was added over ±0.25hours. After addition was complete the reaction mixture was held at 140°C. until the pressure was stable (±0.5 hours). The reaction mixture wascooled to 70° C. and 1580 g of a clear colorless liquid was removed fromthe reactor, which was neutralized with 4.78 g acetic acid: OH value:83.6 mg KOH/g; Acid value: 0.14 mg KOH/g, pH (1% in water): 6.1. Themixture was then cooled to 40° C. and 964.7 g of a clear colorlessliquid was removed from the reactor

Example 6

A four-necked, 500 mL round bottom flask was fitted with a mechanicalstirrer, a thermometer, a stopper and a soxhlet set-up, topped with agas inlet tube and containing 4 Å molecular sieve. The round bottomflask was charged with Example 5C (100 g), lithium bromide (0.51 g) andpara-toluenesulfonic acid monohydrate (1.13 g). Methylal (200 g) wascharged in one addition. The mixture was refluxed at ±50° C. for 12hours. Triethyl amine (0.716 g) was added and the resulting mixture wasstirred for 30 minutes. The mixture was filtered through celite, afterwhich all volatiles were removed at reduced pressure (30 mbar, 50° C.),yielding 106.05 g of a clear, yellow liquid. OH value: 5.4 mg KOH/g;Acid value: 0.58 mg KOH/g; pH (1% in water): 4.8. A 0.3 wt. % solutionof Example 6 in deionized water exhibited a static surface tension of29.71 mN/m. A 0.3 wt. % solution of Example 6 in deionized waterexhibited a dynamic surface tension of 45 mN/ms at 10 ms.

Example 7

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,3,5,5-trimethylhexanol (809.4 g) was charged. A solution of 50 wt % KOHin water (6.5 g) was added and the mixture was heated to 120° C., whilesparging with nitrogen. A vacuum of 0.3 bar was applied and after wasdeionized off during 1 hour, the final water concentration was 0.01 wt%. Propylene oxide (647 g) was added at 120° C. during ±2 hours. Afteraddition was complete the reaction mixture was held at 120° C. until thepressure was stable (±2 hours). The mixture was heated to 140° C. andethylene oxide (986 g) was added during ±2 hours. After addition wascomplete the reaction mixture was held at 140° C. until the pressure wasstable (±0.5 hours). The reaction mixture was cooled to 60° C. andremoved from the reactor, yielding 2413 g of a clear, colorless liquid.OH value: 127.5 mg KOH/g; Base value: 1.04 mg KOH/g.

Example 8

In a 500 ml, four-necked round bottom flask, filled with a nitrogenatmosphere and equipped with a mechanical stirrer, a thermometer, areflux condenser and a gas inlet tube, para-toluenesulfonic acidmonohydrate (1.88 g) and lithium bromide (0.86 g) were dissolved inExample 7 (100 g). The mixture was stirred at room temperature anddimethoxymethane (75.0 g) was added in multiple aliquots. Betweenadditions of dimethoxymethane aliquots, the mixture was alternativelyheated to reflux followed by vacuum distillation, at ±30 mbar and 55-60°C., to remove volatiles. The mixture was reacted for 3 hours. Sodiumcarbonate (1.05 g) was dissolved in the minimum amount of water (±5 mL)and added to the reaction mixture. White solid precipitated out ofsolution. All volatiles were removed under reduced pressure. Theresulting mixture was filtered, yielding 104 g of a clear, slightlyyellow mixture, to which 1 g of water was added. OH number: 19.6 mgKOH/g; Acid number: 0.1 mg KOH/g; pH (1% in water): 7.9. A 0.3 wt. %solution of Example 8 in deionized water exhibited a static surfacetension of 28.51 mN/m. A 0.3 wt. % solution of Example 8 in deionizedwater exhibited a dynamic surface tension of 35 mN/ms at 10 ms.

Example 9

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,octanol (699.6 g) was charged. A solution of 50 wt % KOH in water (5.01g) was added and the mixture was heated to 135° C., while sparging withnitrogen. A vacuum of 0.3 bar was applied and water was removed during 2hour, the final water concentration was 0.08 wt %. Propylene oxide (616g) was added at 120° C. during ±1.5 hours. After addition was completethe reaction mixture was held at 120° C. until the pressure was stable(±2 hours). The mixture was heated to 140° C. and ethylene oxide (934 g)was added during ±2 hours. After addition was complete the reactionmixture was held at 140° C. until the pressure was stable (±0.5 hours).The reaction mixture was cooled to 50° C. and removed from the reactor,yielding 2227.4 g of a clear, colorless liquid. OH value: 137.8 mgKOH/g; Acid value: 0.13 mg KOH/g; pH (1% in water): 6.3.

Example 10

A four-necked, 500 mL round bottom flask was fitted with a mechanicalstirrer, a thermometer, a stopper and a soxhlet set-up, topped with anExample 9 (100 g), lithium bromide (0.825 g) and para-toluenesulfonicacid monohydrate (1.8 g). Methylal (200 g) was charged in one addition.The mixture was refluxed at ±50° C. for 12 hours. Potassium carbonate(0.1.32 g) was added and the resulting mixture was stirred for 30minutes. The mixture was filtered through celite, after which allvolatiles were removed at reduced pressure (30 mbar, 50° C.), yielding105.74 g of a clear yellow liquid. OH value: 25.4 mg KOH/g; Acid value:0.5 mg KOH/g; pH (1% in water): 4.5.

Example 11

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,isononanol (1000 g) was charged. A solution of 50 wt % KOH in water (7.9g) was added and the mixture was heated to 120° C., while sparging withnitrogen. A vacuum of 0.3 bar was applied and water was removed during 2hour, the final water concentration was 0.06 wt %. Propylene oxide (798g) was added at 120° C. during ±1.5 hours. After addition was completethe reaction mixture was held at 120° C. until the pressure was stable(±2 hours). The mixture was heated to 140° C. and ethylene oxide (1211g) was added during ±2 hours. After addition was complete the reactionmixture was held at 140° C. until the pressure was stable (±0.5 hours).The reaction mixture was cooled to 50° C. and neutralized with aceticacid (5.3 g), yielding 2931.8 g of a clear, colorless liquid. OH value:127.1 mg KOH/g; Acid value: 0.09 mg KOH/g.

Example 12

A four-necked, 500 mL round bottom flask was fitted with a mechanicalstirrer, a thermometer, a stopper and a reflux condenser topped with agas inlet tube. The round bottom flask was charged with Example 11 (100g), lithium bromide (0.825) and para-toluenesulfonic acid monohydrate(1.8 g). Methylal (200 g) was charged in one addition. The mixture wasrefluxed at ±50° C. for 12 hours. Sodium carbonate (1.0 g) was added andthe resulting mixture was stirred for 30 minutes. The mixture wasfiltered through celite, after which all volatiles were removed atreduced pressure (30 mbar, 50° C.), yielding 107.13 g of a clear yellowliquid. OH value: 12.3 mg KOH/g; Acid value: 1 mg KOH/g; pH (1% inwater): 4.1.

Example 13

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,isononanol (760.6 g) was charged. A solution of 50 wt % KOH in water(13.9 g) was added and the mixture was heated to 130° C., while spargingwith nitrogen. A vacuum of 0.3 bar was applied and water was removedduring 2 hour, the final water concentration was 0.02 wt %. The mixturewas heated to 160° C. and ethylene oxide (1158.5 g) was added during ±2hours. After addition was complete the reaction mixture was held at 160°C. until the pressure was stable (±0.5 hours). The mixture was cooled to135° C. and propylene oxide (916.5 g) was then added at during ±1.5hours. After addition was complete, the reaction mixture was heated to170-180° C. until the pressure was stable (±0.25 hours). The mixture wasthen cooled to 40° C. and 1004 g of a clear colorless liquid was removedfrom the reactor, which was neutralized with 1.21 g acetic acid: OHvalue: 98.17 mg KOH/g; Acid value: 1.7 mg KOH/g.

Example 14

A four-necked, 500 mL round bottom flask was fitted with a mechanicalstirrer, a thermometer, a stopper and a reflux condenser topped with agas inlet tube. The round bottom flask was charged with Example 13 (100g), lithium bromide (0.6) and para-toluenesulfonic acid monohydrate(1.33 g). Methylal (200 g) was charged in one addition. The mixture wasrefluxed at ±50° C. for 12 hours. Sodium carbonate (0.95 g) was addedand the resulting mixture was stirred for 30 minutes. The mixture wasfiltered through celite, after which all volatiles were removed atreduced pressure (30 mbar, 50° C.), yielding 106.52 g of a cloudy,colorless liquid. OH value: 17.7 mg KOH/g; Acid value: 2.4 mg KOH/g; pH(1% in water): 4.3.

Example 15

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,isononanol (760.6 g) was charged. A solution of 50 wt % KOH in water(13.9 g) was added and the mixture was heated to 130° C., while spargingwith nitrogen. A vacuum of 0.3 bar was applied and water was removedduring 2 hour, the final water concentration was 0.02 wt %. The mixturewas heated to 160° C. and ethylene oxide (1158.5 g) was added during ±2hours. After addition was complete the reaction mixture was held at 160°C. until the pressure was stable (±0.5 hours). The mixture was cooled to135° C. and propylene oxide (916.5 g) was then added at during ±1.5hours. After addition was complete, the reaction mixture was heated to170-180° C. until the pressure was stable (±0.25 hours). The mixture wasthen cooled to 40° C. and 1004 g of a clear colorless liquid was removedfrom the reactor. The product mixture remaining in the reactor washeated to 140° C. and 197.3 g of propylene oxide was added over ±0.25hours. After addition was complete, the reaction mixture was heated to170-180° C. until the pressure was stable (±0.25 hours). The mixture wasthen cooled to 40° C. and 964.7 g of a clear colorless liquid wasremoved from the reactor, which was neutralized with 1.05 g acetic acid:OH value: 89.7 mg KOH/g; Acid value: 1.5 mg KOH/g.

Example 16

A four-necked, 500 mL round bottom flask was fitted with a mechanicalstirrer, a thermometer, a stopper and a reflux condenser topped with agas inlet tube. The round bottom flask was charged with Example 15 (100g), lithium bromide (0.55 g) and para-toluenesulfonic acid monohydrate(1.22 g). Methylal (200 g) was charged in one addition. The mixture wasrefluxed at ±50° C. for 12 hours. Sodium carbonate (1.02 g) was addedand the resulting mixture was stirred for 30 minutes. The mixture wasfiltered through celite, after which all volatiles were removed atreduced pressure (30 mbar, 50° C.), yielding 102.73 g of a clear yellowliquid. OH value: 25.8 mg KOH/g; Acid value: 2.0 mg KOH/g; pH (1% inwater): 4.4.

Example 17

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,isononanol (405.6 g) was charged. A solution of 50 wt % KOH in water(3.9 g) was added and the mixture was heated to 120° C., while spargingwith nitrogen. A vacuum of 0.3 bar was applied and water was removedduring 1 hour, the final water concentration was 0.04 wt. %. Propyleneoxide (484 g) was added at 120° C. during ±1.5 hours. After addition wascomplete the reaction mixture was held at 120° C. until the pressure wasstable (±2 hours). The mixture was heated to 140° C. and ethylene oxide(612 g) was added during ±2 hours. After addition was complete thereaction mixture was held at 140° C. until the pressure was stable (±0.5hours). The reaction mixture was cooled to 50° C. and neutralized with5.03 g 2-ethylhexanoic acid. The product was removed from the reactor,yielding 1482.9 g of a clear, colorless liquid. OH value: 109.5 mgKOH/g; Acid value: 0.12 mg KOH/g.

Example 18

In a 500 ml, four-necked round bottom flask, filled with a nitrogenatmosphere and equipped with a mechanical stirrer, a thermometer, areflux condenser and a gas inlet tube, para-toluenesulfonic acidmonohydrate (1.48 g) and lithium bromide (0.68 g) were dissolved inExample 17 (100 g). The mixture was stirred at room temperature anddimethoxymethane (59.4 g) was added in multiple aliquots. Betweenadditions of dimethoxymethane aliquots, the mixture was alternativelyheated to reflux followed by vacuum distillation, at ±30 mbar and 55-60°C., to remove volatiles. The mixture was reacted for 3 hours. Sodiumcarbonate (0.83 g) was dissolved in the minimum amount of water (±5 mL)and added to the reaction mixture. White solid precipitated out ofsolution. All volatiles were removed under reduced pressure. Theresulting mixture was filtered, yielding 97.78 g of a clear, colorlessmixture, to which 1 g of water was added. OH number: 27.3 mg KOH/g; Acidnumber: 0.6 mg KOH/g; pH (1% in water): 5.3.

Example 19

In a 500 ml, four-necked round bottom flask, filled with a nitrogenatmosphere and equipped with a mechanical stirrer, a thermometer, areflux condenser and a gas inlet tube, para-toluenesulfonic acidmonohydrate (1.5 g) and lithium bromide (0.68 g) were dissolved inExample 4 (100 g). The mixture was stirred at room temperature anddimethoxymethane (59.8 g) was added in multiple aliquots. Betweenadditions of dimethoxymethane aliquots, the mixture was alternativelyheated to reflux followed by vacuum distillation, at ±30 mbar and 55-60°C., to remove volatiles. The mixture was reacted for 3 hours. Sodiumcarbonate (0.83 g) was dissolved in the minimum amount of water (±5 mL)and added to the reaction mixture. White solid precipitated out ofsolution. All volatiles were removed under reduced pressure. Theresulting mixture was filtered, yielding 89.29 g of a yellow, turbidmixture, to which 0.9 g of water was added. OH number: 32.8 mg KOH/g;Acid number: 0.2 mg KOH/g; pH (1% in water): 5.8. A 0.3 wt. % solutionof Example 19 in deionized water exhibited a static surface tension of29.08 mN/m. A 0.3 wt. % solution of Example 19 in deionized waterexhibited a dynamic surface tension of 40 mN/ms at 10 ms.

Example 20

In a clean and dry, four liter, steel pressure reactor, equipped with amechanical stirrer, a nitrogen inlet, a vacuum outlet, an ethyleneoxide/propylene oxide inlet, a thermometer and a pressure sensor,isononanol (759 g) was charged. A solution of 50 wt % KOH in water (6.4g) was added and the mixture was heated to 130° C., while sparging withnitrogen. A vacuum of 0.3 bar was applied and water was removed during 2hour, the final water concentration was 0.09 wt. %. The mixture washeated to 140° C. and ethylene oxide (464 g) was added during ±2 hours.After addition was complete the reaction mixture was held at 140° C.until the pressure was stable (±0.5 hours). The mixture was cooled to120° C. and propylene oxide (611.5 g) was added during +1.5 hours. Afteraddition was complete the reaction mixture was held at 120° C. until thepressure was stable (±4 hours). The mixture was heated to 140° C. andethylene oxide (696 g) was added during ±2 hours. After addition wascomplete the reaction mixture was held at 140° C. until the pressure wasstable (±0.5 hours). The reaction mixture was cooled to 50° C. and theproduct was removed from the reactor, yielding 2496 g of a clear,colorless liquid. OH value: 117.5 mg KOH/g; Base value: 0.02 meq/g; pH(1% in water): 9.8.

Example 21

In a 500 ml, four-necked round bottom flask, filled with a nitrogenatmosphere and equipped with a mechanical stirrer, a thermometer, areflux condenser and a gas inlet tube, para-toluenesulfonic acidmonohydrate (2.37 g) and lithium bromide (1.08 g) were dissolved inExample 20 (150 g). The mixture was stirred at room temperature anddimethoxymethane (94.93 g) was added in multiple aliquots. Betweenadditions of dimethoxymethane aliquots, the mixture was alternativelyheated to reflux followed by vacuum distillation, at ±30 mbar and 55-60°C., to remove volatiles. The mixture was reacted for 3 hours. Sodiumcarbonate (1.32 g) was dissolved in the minimum amount of water (±4 mL)and added to the reaction mixture. White solid precipitated out ofsolution. All volatiles were removed under reduced pressure. Theresulting mixture was filtered, yielding 145.9 g of a colorless, clearmixture, to which 1.5 g of water was added. OH number: 36.9 mg KOH/g;Acid number: 0.1 mg KOH/g; pH (1% in water): 9.6.

Example 22 Test Procedure for Testing Foaming of Wetting Agents inDeionized Water

Low foam wetting agents described in the previous examples were measuredaccording to the foam testing procedure described herein. Foam test wasalso carried out on a number of commercial wetting agents. Theseinclude: (1) an acetylenic diol gemini surfactant composition (Surfynol™104H), (2) an alkyl ethoxylate surfactant composition (Multiwet™ SU) and(3) an alkyl phenol ethoxylate (Triton™ CF10).

The results are summarized in Table 1.

TABLE 1 Foam Test Data Foam Height Foam Height Immediate after 5 mins.wait time after blowing air, blowing air, Example No. cm ± 0.2 cm cm ±0.2 cm 1 0.42 0.00 3 0.00 0.00 5 12.75 0.00 6 1.36 0.00 7 1.27 0.42 80.00 0.00 9 17.00 1.70 10 0.00 0.00 12 0.00 0.00 15 4.76 0.85 14 0.000.00 15 0.00 0.00 16 0.00 0.00 17 19.00 1.70 18 0.00 0.00 4 18.20 1.7019 4.00 0.30 20 18.20 0.90 21 0.00 0.00 Gemini Diol 0.00 0.00 AlkylEthoxylate 17.00 3.40 Alkyl Phenol 17.00 0.85 Ethoxylate

Example 23

DST measurements were evaluated for an inventive example and threecommercial examples: (1) Example 8, (2) an acetylenic diol geminisurfactant composition (Surfynol™ 104H), (3) an alkyl ethoxylatesurfactant composition (Multiwet™ SU) and (4) an alkyl phenol ethoxylate(Triton™ CF10). The testing was done using a Kruss™ BP2 BubbleTensiometer. As much as was possible, solution concentrations were keptthe same or very close. Three of the wetting agents had concentrationsof 0.25%-0.30% in deionized water. The gemini diol had limitedsolubility in water and could only be added at a concentration of 0.1%.Surface ages were increased from 10 ms up to about 50,000 ms. Areference material to be used for comparison is deionized water whichhas a DST result of 72-73 mN/m.

The results from the DST testing are shown in the FIGURE. Surface age inmilliseconds (ms) is shown on the X-axis, and the solution surfacetension is shown on the Y-axis. The alkyl phenol ethoxylate and thegemini diol wetting agents do not provide the same level of surfacetension reduction compared to the other two. Their surface tensionreduction does improve with increasing surface age and eventually levelsout at about 34 mN/m at surface ages greater than 5000 ms. The wettingagent of Example 8 provides better surface tension reduction than thegemini diol and alkyl phenol ethoxylate at all measured surface ages,and it is competitive with the alkyl ethoxylate at surface ages greaterthan 500 ms.

SST measurements were performed on the four wetting agents describedabove. All four wetting agents were evaluated at the 0.3% concentrationin deionized water. The measured SST values of the four wetting agentsare as follows:

Example 8 27.2 mN/m Alkyl phenol ethoxylate 33.6 mN/m Alkyl ethoxylate26.3 mN/m Gemini diol 32.1 mN/mExample 8 has a lower SST than the alkyl phenol ethoxylate and thegemini diol, and is close to the SST of alkyl ethoxylate. The alkylethoxylate has an SST which is 1.1 mN/m lower than the result forExample 8, however, the wetting agent alkyl ethoxylate suffers from theadverse defect of producing much foam during its use in coatingpreparations and applications. deionized

Example 24 Wetting Performance on Wood Lacquer

Varnish coated wood surfaces may sometimes be low surface energy anddifficult to wet-out. For this reason wetting agents are added to waterbased wood coating lacquers to improve substrate wetting. Wood lacquersare typically applied by brush, spray, and sometimes by roller.

These application processes can incorporate foam into the lacquercoating. Foam trapped in dried film adversely impacts the film'sprotective property as well as its appearance. Table 2 shows the clearwood lacquer formula which was used to evaluate the performance of fourtypes of wetting agents.

TABLE 2 Clear wood lacquer formula. Raw Material Pounds FunctionSupplier Resin: Essential 88.45 Binder Essential Polymers R6010 Water4.65 Solvent — Dowanol ™ DPM 3.14 Coalescent DOW Chemical Dowanol ™ DPnB3.14 Coalescent DOW Chemical Test Sample 0.30 Wetting Agent variousRheolate ® 658 0.32 Associative Elementis Specialties Thickener Total100.00 — —

Application foam tests were carried out for the four wetting agentsdescribed in example 24, as well as a control without wetting agent, asper Test methods A1 and A2. The amount of foam generated duringapplication by each of the different application methods were rankedrelative to the control.

Table 3 shows results for the different modes of application for thecontrol and four wetting agent modified lacquers. Each of the lacquershad comparable viscosity and gloss. The major differences between thewetting agents stand out in the foam generated during the differentmethods of application. Based on the results for brush and rollerapplications, the gemini diol and the Example 8 wetting agent appear tocause fewer problems associated with foaming. The two remaining wettingagents could be problematic during roller application.

TABLE 3 Paint and dry film test properties of the different wettingagents in the clear wood lacquer formula. Alkyl Control Example PhenolAlkyl Gemini (none) #8 Ethoxylate Ethoxylate Diol Wetting Agent 3401-223401-23-B 3401-23-C 3401-23-D 3401-23-E Brookfield 107 107 107 102 110Viscosity (50 rpm, cps) Gloss by Drawdown 20° 76 76 75 77 77 60° 90 9091 91 91 Gloss by Spray 20° 72 75 75 75 74 60° 90 91 91 90 91Wettability 3 8 7 9 4 Test F Foaming by 8 7 6 3 8 Brushing Foaming by 76 5 1 6 Roller Foaming by 9 9 9 9 9 Spray Rating: 10—Excellent; 7—Good;4—Fair; 1—Poor.

Example 25 Pigment Wetting

Wetting of pigments is essential to get optimum pigment dispersion.Pigment particles present as agglomerates are surrounded with air thatmust be displaced by liquid for wetting of the particles to take place.The wetting step involves replacing adsorbed materials on the pigmentsurface with liquid. If the surface tension of the liquid is higher thanthe surface energy of the pigment then it will not wet the pigmentsurface.

Water alone is unable to wet the surface of many pigments due to itshigher surface tension than the surface energy of the pigments. Wettingagents are added to lower the surface tension of water and aid pigmentwetting by adsorbing and orienting on the liquid-air interface resultingin lowering the interfacial tension.

Wetting agents apart from reducing the surface tension of water alsohave a tendency of stabilizing foam. Foam generated during productioncan interfere with the dispersion process affecting opacity and colordevelopment, increase production time and compromising product quality.

The ability of the inventive wetting agents to provide adequate wettingof pigments without excessive foam production was demonstrated in thegrind stage of a typical waterborne coating. The grind stage involvesthe wetting and dispersion of TiO₂, resulting in a TiO₂ slurry. Theperformance of the inventive wetting agent was compared to thecommercial wetting agents listed in Table 3.

Table 4 shows the formulation used to make a TiO₂ slurry. Wetting agentswere added at 0.97% actives on TiO₂ weight. Defoamer was intentionallyleft out to capture the foaming tendency differences of the wettingagents.

TABLE 4 Titanium Dioxide Slurry Formula Raw Material Pounds FunctionSupplier Water 26.00 Solvent — Proxel ™ GXL 0.20 Biocide Arch ChemicalsNuosperse ® FX665 1.50 Dispersant Elementis Specialties Non IonicSurfactant 0.70 Wetting Agent Various suppliers TiO₂ DuPont R706 71.60Pigment Du Pont Mix using a Dispermat ™ @ 500 rpm for 10 mins; tip speed= 1.31 m/s Check grind Total 100.00

The foaming tendency of each wetting agent used in the TiO₂ slurry wastested by roller application, according to Test A1.

Table 5 shows the evaluation results of TiO₂ slurries based on fourwetting agents. Each of the slurries had comparable grind, viscosity andgloss. The major differences between the wetting agents stand out in thefoam generated during the making of TiO₂ slurry. The gemini diol and theExample 8 wetting agent resulted in significantly less foam than thealkyl phenol ethoxylate and alkyl ethoxylate based slurry.

The Gemini diol based TiO₂ slurry showed excessive grit upon drawingdown on a Leneta Form 1B opacity chart using a 3 mil Bird applicator.Grit appears to be small gel particles which could not be captured onthe grind gage. The soft gel particles may be related to the lowsolubility of gemini diol in water. The low foaming characteristics ofgemini diol could possibly be due to its low water solubility.

Excess foam generated during the grind stage may result in prolongedgrind time resulting in the loss of production time and an inferiorquality of the finished product. Addition of excess defoamer to overcomefoam will increase product cost and possibly compromise the final filmproperties.

TABLE 5 Test results of the different wetting agents in the TiO₂ Slurryformula. Alkyl Phenol Alkyl Gemini Wetting Agent Example 8 EthoxylateEthoxylate Diol Brookfield Viscosity 354  4804  3264  3124  (50 rpm,cps) Gloss by Drawdown 20° 70+ 70+ 70+ 70+ 60° 90+ 90+ 90+ 90+ HegmanGrind 8 8 7 7 Draw Down Appearance Smooth Smooth Smooth Gritty Foamingby Roller 9 1 1 9 Rating: 10—Excellent; 7—Good; 4—Fair; 1—Poor.

Example 26 Application in Decorative Coatings—

Water based coatings are formulated with various ingredients such assolvent, binder, pigments or fillers, surfactants-wetting agents anddispersant, film formers, biocides, defoamers, and rheology modifiers.Wetting agents are used for various purposes in waterborne coatings.These include pigment wetting for optimum dispersion of pigments thatprovide control of opacity and color development. They promote wettingof low surface energy substrates resulting in improved adhesion to suchsurfaces. Wetting agents can also be used as leveling aids.

Because water based coatings are marketed as eco-friendly coatings,solvents traditionally used in these coatings have either been removedor significantly reduced in concentration. As a result, the coatingsface increased challenges in areas such as freeze thaw stability,shorter open time, and in can paint skinning. Wetting agents are helpfulto some extent in such demanding performance properties. However,wetting agents tend to make the coating water sensitive resulting inpoor blister and blush resistance, surfactant leaching, foaming,burnishing, film softening and they affect stain resistance. Due tothese concerns, the inventive wetting agent was evaluated in a typicalwaterborne coating and compared to the commercial wetting agents listedin Table 3. Table 6 shows the formulation used to make a test decocoating. Sample wetting agents were added in the let down at 0.30%actives on total paint weight. Ideally the wetting agent should be addedbefore the pigments for wetting the pigments-essential in the dispersionprocess. However, for this evaluation the wetting agents were added inthe letdown to 25 minimize process variability. The formulation had11.11 pounds/gallon; 53.4 wt. % solids; 37.4 vol. % solids; 27.9% PVC;0.2 lbs./gal VOC; and 21.0 g/1l VOC.

TABLE 6 Formulation of Deco Coating Raw Material Pounds FunctionSupplier Water 15.66 Solvent — Proxel ™ GXL 0.10 Biocide Arch ChemicalsNuosperse ® 1.00 Dispersant Elementis Specialties FX665 Mix low speedfor 2-3 mins. Titanium Dioxide 27.50 Hide DuPont R706 Minex ® 7 2.50Sheen Control Unimin Corporation Mix @ 1500 rpm for 5 mins; tip speed6.28 m/s. Grind 6+ at 1000 rpm; tip speed 4.19 m/s Ammonium 0.15 BufferSigma Aldrich Hydroxide Mix 2-3 mins. Rhoplex ™ HG706 49.34 Resin DOWChemicals Dapro ® DF39 0.10 Defoamer Elementis Specialties Texanol 0.60Coalescent Eastman Chemical Company Maintain 1000 rpm; tip speed 4.19m/s. Add following ingredients Rheolate ® HX6010 2.20 Rheology ElementisSpecialties Modifier Rheolate ® CVS10 0.50 Rheology ElementisSpecialties Modifier Mix 5 mins. Then add Dapro ® DF39 0.35 DefoamerElementis Specialties Total 100.00

A master batch, without wetting agent, was made and then split in equalparts. Defoamer was intentionally kept at a minimum in the formula tocapture the foaming tendency differences of the wetting agents.

Table 7 shows the evaluation results of the test deco coating based onfour wetting agents. Each of the coatings had comparable performance insome application properties. The differences between the wetting agentsare seen in their foaming characteristics, color acceptance, tintstrength, freeze thaw stability, sag, washability, and early blockresistance. Each property was measured by methods described herein.

TABLE 7 Evaluation of deco coating containing different wetting agents.Alkyl Phenol Alkyl Gemini Wetting Agent None Example 8 EthoxylateEthoxylate Diol D562 Viscosity Stormer (KU) 105 101 99 97 104 D4287 (1)Cone & Plate ICI (Poise) 1.57 1.55 1.53 1.42 1.60 D523 (2) Gloss(60°/85°) 39/73 39/74 38/74 43/76 40/72 D4400 Sag mils 18 16 12 12 14Drips Drips D4062 Leveling 9 9 9 9 9 Foaming - Roller 8 7.5 6 6 8 D2486Scrub Cycles 449 456 462 450 587 D4828 Washability 7 6.5 6 5 5.5 D7190Surfactant Leaching Pass Pass Pass Pass Pass D714 Blister Resistance (2hrs. 10 10 10 10 10 water contact) Blush Resistance (2 hrs. 9 9 9 9 9water contact) Tint Strength 100.00 99.12 99.37 99.05 99.91 Test C ColorAcceptance 9 9 9 9 9 D4946 Early 7.7 7.3 8.3 6.0 6.7 Block Resistance(24 hrs cure; avg. of 3) D6736 (3) Burnish Resistance (% Standard No NoNo No change in gloss) Change Change Change Change STABILITY DATA Aged @Viscosity (KU; 12 days) 93 95 94 91 97 60° C. 24 Hrs. Foam 8 7.5 6 6 8ASTM# 12 Days Foam 8 7 6 6 6 D1849 Roller Viscosity (KU; 12 days) 104102 99 100 106 Stability 24 Hrs. Foam 8 7 5 4 7 Test B 12 Days Foam 8 75 4 4 Freeze 1^(st) Cycle Fail Pass Pass Pass Fail Thaw 2^(nd) Cycle NAPass Pass Pass NA ASTM 3^(rd) Cycle NA Pass Pass Pass NA #D8020 (4)Rating: 10—Excellent; 7—Good; 4—Fair; 1—Poor.

Example 27 Water Droplet Spreading Analysis

In order to evaluate the capacity of the inventive wetting agent toimpart wetting properties to a water based formulation, a simpleexperiment was carried out, in which dilute aqueous solutions of wettingagent were prepared and applied to a low energy solid substrate. Thedegree to which the applied solution spread on the substrate was used asa measure of the performance of the wetting agent. Similar solutions ofcommercial wetting agents listed in Table 3 were also prepared and addedto the substrate in a similar way. A comparison of the spreading ratesfor these solutions provided a relative measure of the wettingperformance for these surfactants, shown in Table 8.

TABLE 8 Test Results Liquid Deposited Liquid Dimensions Blank Test PanelDimensions  (95 mm × 145 mm) Deionized Water (reference) 21 mm × 22 mmExample 8 71 mm × 91 mm 0.3% Aq Alkyl Phenol Ethoxylate 38 mm × 41 mm0.3% Aq Alkyl Ethoxylate 76 mm × 105 mm 0.3% Aq Gemini Diol 31 mm × 37mm 0.3% Aq

From the results listed in Table 8 both the alkyl phenol ethoxylate andgemini diol only provide slight wetting spreading improvement over theblank water sample. The inventive composition and the alkyl ethoxylateboth provide much better wetting spreading of the liquid. The rankingresults from this spreading experiment are: (1) alkyl ethoxylate; (2)inventive composition; (3) alkyl phenol ethoxylate which isapproximately equal to (4) gemini diol. These results are in the samerelative order of the measured static surface tension results and thedynamic surface tension results taken from the 30,000-50,000milliseconds (ms) range of the DST curve.

The present disclosure may be embodied in other specific forms withoutdeparting from the spirit or essential attributes of the invention.Accordingly, reference should be made to the appended claims, ratherthan the foregoing specification, as indicating the scope of thedisclosure. Although the foregoing description is directed to thepreferred embodiments of the disclosure, it is noted that othervariations and modification will be apparent to those skilled in theart, and may be made without departing from the spirit or scope of thedisclosure.

1-14. (canceled)
 15. A wetting agent comprising a composition accordingto Formula (I):

wherein R¹ is selected from a branched alkyl group or linear alkyl groupor a cycloaliphatic group or an aromatic group, each having 6 to 15carbon atoms; R² is selected from hydrogen, methyl, or ethyl; R³ ismethyl; R⁴ is hydrogen; R⁵ is selected from methyl or ethyl; x rangesfrom 0 to 5; y ranges from 2 to 5; z ranges from 3 to 10; with theproviso that when x ranges from 1 to 5, R² is different from R³; andwith the proviso that when x=0, R³ is different from R⁴.
 16. The wettingagent according to claim 15, further comprising a composition accordingto Formula (II):

wherein R⁶ is the same as R¹, R⁷ is the same as R², R⁸ is the same as R³and R⁹ is the same as R⁴, a equals x, b equals y and c equals z.
 17. Thewetting agent according to claim 15, wherein R¹ is selected from abranched alkyl group or linear alkyl group or a cycloaliphatic group oran aromatic group, each having 6 to 10 carbon atoms.
 18. The wettingagent according to claim 17, where in R¹ is selected from nonyl,isononyl, 3,5,5-trimethyl hexyl, octyl, 2-methyl heptyl, 2-ethyl hexyl,2,2,4-trimethyl pentyl, 4-methyl pentyl, heptyl, hexyl and combinationsthereof.
 19. The wetting agent according to claim 15, wherein a 0.3 wt.% solution of the wetting agent composition in aqueous solution has adynamic surface tension ranging from 50 mN/m to 25 mN/m at 1000 ms orless surface age.
 20. The wetting agent according to claim 15, wherein a0.3 wt. % solution of the wetting agent in aqueous solution has a staticsurface tension ranging from 45 mN/m to 20 mN/m.
 21. The wetting agentaccording to claim 15, wherein a 0.3 wt. % solution of the wetting agentin aqueous solution has a foaming value less than 17 cm when measured ata concentration of 0.3 wt. % according to the foam test procedure andhas a foaming value less than 3 cm when measured at a concentration of0.3 wt. % 5 minutes after completion of the foam test procedure.